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通过转移氢化进行催化羰基加成:与预制有机金属试剂的不同之处。

Catalytic carbonyl addition through transfer hydrogenation: a departure from preformed organometallic reagents.

作者信息

Bower John F, Kim In Su, Patman Ryan L, Krische Michael J

机构信息

University of Texas at Austin, Department of Chemistry and Biochemistry, 1 University Station, A5300, Austin, TX 78712-1167, USA.

出版信息

Angew Chem Int Ed Engl. 2009;48(1):34-46. doi: 10.1002/anie.200802938.

DOI:10.1002/anie.200802938
PMID:19040235
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC2775511/
Abstract

Classical protocols for carbonyl allylation, propargylation and vinylation typically rely upon the use of preformed allyl metal, allenyl metal and vinyl metal reagents, respectively, mandating stoichiometric generation of metallic byproducts. Through transfer hydrogenative C-C coupling, however, carbonyl addition may be achieved from the aldehyde or alcohol oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. Here, we review transfer hydrogenative methods for carbonyl addition, which encompass the first catalytic protocols enabling direct C-H functionalization of alcohols.

摘要

传统的羰基烯丙基化、炔丙基化和乙烯基化反应通常分别依赖于使用预制的烯丙基金属、联烯基金属和乙烯基金属试剂,这就要求化学计量地生成金属副产物。然而,通过转移氢化C-C偶联反应,可以在不存在化学计量的有机金属试剂或金属还原剂的情况下,从醛或醇的氧化态实现羰基加成。在此,我们综述了羰基加成的转移氢化方法,其中包括实现醇的直接C-H官能团化的首批催化反应。

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2
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Ruthenium-catalyzed C-C bond forming transfer hydrogenation: carbonyl allylation from the alcohol or aldehyde oxidation level employing acyclic 1,3-dienes as surrogates to preformed allyl metal reagents.钌催化的碳-碳键形成转移氢化反应:以无环1,3-二烯作为预制烯丙基金属试剂的替代物,从醇或醛氧化态进行羰基烯丙基化反应。
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Enantioselective iridium-catalyzed carbonyl allylation from the alcohol or aldehyde oxidation level using allyl acetate as an allyl metal surrogate.使用乙酸烯丙酯作为烯丙基金属替代物,从醇或醛氧化水平进行对映选择性铱催化的羰基烯丙基化反应。
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